N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N&#39;-benzoylurea insecticides

ABSTRACT

N-[(Alpha-perhaloalkylbenzyloxy)pyridyl]-N&#39;-benzoylurea compounds of the following structural formula are useful insecticides: ##STR1## in which R A  is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy; 
     R B  is selected from -hydrogen and -halogen; 
     R C  and R D  are both -hydrogen or together constitute a --COCO-- bridge; 
     R.sub.α  is a perhaloalkyl substituent; 
     R 3  is selected from the group consisting of -hydrogen, -halogen and -phenylthio; 
     R 4  is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino; or 
     R 3  and R 4  at adjacent ring positions constitute a --OCH 2  O--, --CH 2  C(CH 3 ) 2  O--, or --CF 2  CF 2  O-- bridge; and 
     R 5  is -hydrogen or -lower alkyl.

This is a continuation-in-part of application Ser. No. 801,365 filedNov. 25, 1985, now abandoned.

The invention pertains to the field of benzoylurea insecticides; morespecifically, it pertains to novelN-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea insecticides,processes and intermediates thereto, insecticidal compositionscontaining such benzoylurea compounds, and to the use of such compoundsfor controlling insects.

Certain N-[substituted pyridinyl]-N'-benzoylurea compounds are known asinsecticides. For example, U.S. Pat. No. 4,173,639 and U.S. Pat. No.4,264,605 describe such N'-benzoylurea compounds carrying a N-pyridylsubstituent in which the pyridine ring also contains a hydrocarbyloxygroup. It is reported that compounds of this type affect insects byinterfering with their metamorphosis; that is, they disrupt the normalgrowth and development pattern.

According to the present invention, adding an alpha-perhaloalkylsubstituent to the benzyl group provides insecticides with enhancedactivity, controlling certain insects at application rates as low as 1ppm. Accordingly, theN-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds ofthis invention are described by the formula ##STR2## in which

R_(A) is selected from the group consisting of -hydrogen, -halogen,-lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;

R_(B) is selected from -hydrogen and -halogen;

R_(C) and R_(D) are both -hydrogen or together constitute a --COCO--bridge;

R.sub.α is a perhaloalkyl substituent;

R₃ is selected from the grup consisting of -hydrogen, -halogen and-phenylthio;

R₄ is selected from the group consisting of -hydrogen, -halogen, -loweralkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -loweralkylthio, -lower alkylsulfonyl, and -diallylamino; or

R₃ and R₄ at adjacent ring positions constitute a --OCH₂ O--, --CH₂C(CH₃)₂ O--, or --CF₂ CF₂ O-- bridge; and

R₅ is -hydrogen or -lower alkyl.

The terms "halo" and "halogen" when employed herein mean fluorine,chlorine or bromine. The term "lower" modifying "alkyl," "alkoxy," andthe like implies a straight or branched hydrocarbon chain of 1-6,preferably 1-3, carbon atoms; "halo" coupled with another term means oneor more hydrogen atoms has been replaced by halogen; "perhalo" coupledwith another term means all the hydrogen atoms have been replaced byhalogen.

Among the aforesaid compounds, the most attractive insecticides resultwhen R_(A) and R_(B) are in the 2- and 6-positions, respectively. Inaddition, N-(3-pyridinyl) compounds are preferred, with R₅ at the5-position. Additionally, the preferred compounds have the R₃ and R₄substituents in the 3- and 4-positions, respectively. Specific compoundsof interest includeN-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide,N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-fluorobenzamide,N-[[[[2-[1-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)]-2,2,2-trifluoroethoxy]-pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]-pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,N-[[[[2-[1-(1,3-benzodiox-5-yl)-2,2,3,3,4,4,4-heptafluorobutoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,N-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,1-[(2,6-difluorophenyl)carbonyl]-3-[2-[1-(1,3-benzodiox-5-yl)-2,2,2-trifluoroethoxy]pyridin-5-yl]imidazolidinetrione,1-[(2,6-difluorophenyl)-carbonyl]-3-[[2-(1-phenyl-2,2,2-trifluoroethoxy)-3-methyl]pyridin-5-yl]imidazolidinetrione,N-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,andN-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]-amino]carbonyl]-2-chlorobenzamide.

Also within the contemplation of the instant invention are insecticidalcompositions comprising an insecticidally effective amount of at leastone of the aforesaid benzoylurea compounds in admixture with anagriculturally acceptable carrier. In addition, this invention includesa method of controlling insects which comprises applying to plants uponwhich the insects feed and where control is desired an insecticidallyeffective amount of at least one of the afoesaidN-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds.

The compounds of this invention can be prepared using general techniquesdisclosed in U.S. 4,013,717, viz: ##STR3## Preparation of the compoundsof this invention will be clarified by reference to the followingExamples.

EXAMPLE 27N-[[[[2-[1-(2,3-Dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide

5-Amino-3-methyl-2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]pyridinewas prepared from2,2,3,3,3-pentafluoro-1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)propan-1-one,by the method of Example 42. 2-Chloro-3-methyl-5-nitropyridine was usedin place of 2-chloro-5-nitropyridine.

In a manner similar to Example 42 the reaction of 2-chlorobenzamide (0.6g, 0.0037 mole), first with oxalyl chloride (0.5 g 0.0037 mole) inmethylene chloride (10 ml) and toluene (70 ml), followed by reactionwith5-amino-3-methyl-2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]pyridine(1.5 g, 0.0037 mole), yielded 1.6 g ofN-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]-amino]carbonyl]-2-chlorobenzamideas a solid (mp 141°-143° C.). The nmr and ir spectra were consistentwith the proposed structure.

Analysis: Calc'd for C₂₇ H₂₃ ClF₅ N₃ O₄ : C 55.54; H 3.97; Found: C56.10; H 4.17.

EXAMPLE 42N-[[[2-[1-(3,4-Dichlorophenyl)-2,2,2-trifluoroethoxy]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide

Under a dry nitrogen atmosphere a mixture of3,4-dichloro-alpha,alpha,alpha-trifluoroacetophenone (6.4 g, 0.026 mole)and sodium borohydride (2.0 g, 0.052 mole) in ethanol (100 ml) wasstirred at room temperature for approximately 18 hours. The solvent wasevaporated under reduced pressure leaving a residue which was dissolvedin water. The resultant solution was extracted with two 100 ml portionsof methylene chloride. The combined extracts were dried over anhydrousmagnesium sulfate and filtered. The filtrate was evaporated underreduced pressure, yielding 6.4 g of1-(3,4-dichlorophenyl)-2,2,2-trifluoroethanol.

Under a dry argon atmosphere a solution of 2-chloro-5-nitropyridine (1.6g, 0.010 mole) and 1-(3,4-dichlorophenyl)-2,2,2-trifluoroethanol (2.5 g,0.010 mole) in dimethyl sulfoxide (50 ml) was stirred for five minutes.Potassium carbonate (1.6 g, 0.011 mole) was added to the mixture in oneportion. The resultant mixture was stirred at room temperature forapproximately 18 hours. The mixture was transferred to a separatoryfunnel to which was added 50 g of ice and 75 ml of a 2N aqueous sodiumhydroxide solution. This aqueous mixture was extracted with two 200 mlportions of diethyl ether. The combined extracts were dried overanhydrous magnesium sulfate and filtered. The solvent was evaporatedfrom the filtrate under reduced pressure, leaving an oil. Purificationof this oil by column chromatography on silica gel yielded 3.3 g of2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]-5-nitropyridine.

Hydrogenation of2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]-5-nitropyridine (2.7 g,0.0074 mole) with platinum oxide (0.3 g, 0.0013 mole) in methanol (50ml) yielded 2.5 g of5-amino-2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridine.

A stirred mixture of 2,6-diflurorobenzamide (0.56 g, 0.0036 mole),oxalyl chloride (0.45 g, 0.0036 mole), and methylene chloride (10 ml) intoluene (70 ml) was heated at reflux for three hours. Approximately 10ml of solvent was removed by distillation under reduced pressure. Asolution of5-amino-2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridine (1.2 g,0.0036 mole) in toluene (35 ml) was added to the reaction mixtue. Theresultant solution was stirred at room temperature for approximately 18hours. Most of the solvent was evaporated under reduced pressure,leaving a liquid residue. About 150 ml of n-heptane was added to theresidue, and the mixture was stirred at room temperature, slowly forminga precipitate. The mixture was cooled in dry ice before collecting theprecipitate by filtration. A total of 1.65 g ofN-[[[2-[-1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamidewas collected (mp 171°-172° C.). The nmr and ir spectra were consistentwith the proposed structure.

Analysis: Calc'd for C₂₁ H₁₂ Cl₂ F₅ N₃ O₃ : C 48.48; H 2.33; Found: C48.62; H 2.60.

EXAMPLE 66N-[[[2-[1-(2,2,3,3-Tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide

5-Amino-3-methyl-2-[1-(2,2,3,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]pyridinewas prepared from1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethanone by themethod of Example 42. The latter starting material was obtained asfollows:

Into a pressure bottle was placed 2-chloro-4-nitrophenol (15.0 g, 0.086mole), potassium carbonate (11.9 g, 0.86 mole), propanethiol (1.5 g,0.02 mole), 1,2-dibromotetrafluoroethane (33.7 g, 0.13 mole), andN,N-dimethylformamide (115 ml). The pressure bottle was sealed, and themixture was stirred at 50° C. for 48 hours. The pressure bottle wascooled to room temperature, opened, and the contents poured into aseparatory funnel. Approximately 200 ml of a 2N aqueous sodium hydroxidesolution was added to the separatory funnel. The resultant mixture wasextracted with four 300 ml portions of diethyl ether. The extracts werecombined and washed with two 100 ml portions of a 2N aqueous sodiumhydroxide solution. The washed extract was dried over anhydrousmagnesium sulfate and filtered. The filtrate was evaporated underreduced pressure, leaving an oil. The reaction described above wasrepeated three additional times. The residual oils from the fourexperiments were combined and purified by column chromatography onsilica gel, eluting with n-heptane:toluene (95:5), yielding 57.6 g of3-chloro-4-bromo-1,1,2,2-tetrafluoroethoxy)nitrobenzene as an oil.

Into a pressure bottle were placed3-chloro-4-(2-bromo-1,1,2,2-tetrafluoroethoxy)nitrobenzene (10.0 g,0.028 mole), copper powder (9.0 g, 0.14 mole 200 mesh), 2,2'-bipyridyl(0.45 g, 0.0028 mole), and dimethylsulfoxide (40 ml). The pressurebottle was sealed and the reaction mixture was stirred at 190°-195° C.for two hours. The pressure bottle was cooled to room temperature,opened, and the contents poured, into a separatory funnel. Approximately200 ml of a 2N hydrochloric acid solution was added to the separatoryfunnel. The mixture was extracted with three 150 ml portions of diethylether. The extracts were combined and washed in succession with 200 mlof a 2N hydrochloric acid solution, 200 ml of a saturated aqueous sodiumchloride solution, and 200 ml of a 2N aqueous sodium hydoxide solution.The washed extract was dried over anhydrous magnesium sulfate andfiltered. The solvent was evaporated under reduced pressure, leaving anoil. The reaction described above was repeated six additional times. Theresidual oils from the seven experiments were combined and subjected tocolumn chromatography on silica gel, eluting with toluene, yielding ayellow oil. This oil was dissolved in 125 ml methylcyclohexane, and thesolution was placed in a freezer for approximately 18 hours. Crystalsformed and were collected by filtration, yielding 20.7 g of2,2,3,3-tetrafluroro-5-nitrobenzofuran. The filtrate was evaporatedunder reduced pressure, leaving an oil. Distillation of this oil underreduced pressure provided an additional 3.0 g of product (bp 75° C./0.2mm Hg).

Hydrogenation of 2,2,3,3-tetrafluoro-5-nitrobenzene (10.0 g, 0.042 mole)with a catalytic amount of platinum oxide (0.5 g) in methanol (200 ml)produced 8.6 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.

A stirred mixture of 5-amino-2,2,3,3-tetrafluorobenzofuran (5.0 g, 0.024mole) and hydrobromic acid (7.3 ml of a 48% aqueous solution) and water(10 ml) was cooled to 3° C. in an ice bath. While maintaining atemperature of less than 5° C., a solution of sodium nitrite (1.7 g,0.024 mole) in water was added. After complete addition this mixture wasstirred for a brief period, then was added slowly to a stirred,refluxing mixture of cuprous bromid (6.9 g, 0.024 mole) in hydrobromicacid (10 ml of a 48% aqueous solution). After complete addition themixture was stirred at reflux for 20 minutes, then allowed to cool toroom temperature. The reaction mixture was poured into a separatoryfunnel and diluted with ice water. This mixture was extracted severaltimes with diethyl ether. The extracts were combined and washed firstwith 100 ml of an aqueous saturated sodium chloride solution, then withtwo 100 ml portions of a 2 N aqueous sodium hydroxide solution. Thewashed organic phase was dried over anhydrous magnesium sulfate andfiltered. The filtrate was evaporated at atmospheric pressure, yielding5.9 g of 5-bromo-2,2,3,3-tetrafluorobenzofuran as an oil.

The reaction of 5-bromo-2,2,3,3-tetrafluorobenzofuran (5.3 g, 0.02 mole)with magnesium turnings (0.48 g) in dry diethyl ether was followed byreaction with N-methoxy-N-methyltrifluoroacetamide (3.5 g, 0.022 mole),yielding 5.3 g of1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethanone.

In a manner similar to Example 42 the reaction of 2,6-difluorobenzamide(0.3 g, 0.0019 mole), first with oxalyl chloride (0.3 g, 0.0021 mole) inmethylene chloride (5 ml) and toluene (50 ml), followed by reaction with5-amino-3-methyl-2-[1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]pyridine(0.8 g, 0.0019 mole) yielded 0.8 g ofN-[[[[2-[1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]-3-methyl]pyridine-5-yl]amino]carbonyl]2,6-difluorobenzamideas an oil. The nmr and ir spectra were consistent with the proposedstructure.

Analysis: Calc'd for C₂₄ H₁₄ F₉ N₃ O₄ : C 49.75; H 2.43; Found: C 47.47;H 2.26.

EXAMPLE 841-[(2,6-Difluorophenyl)carbonyl]-3-[2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridin-5-yl]imidazolidinetrione

To a stirred solution ofN-[[[2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridin-5-yl]amino]-carbonyl]2,6-difluorobenzamide(1.0 g, 0.002 mole) in 1,2-dichloroethane (10 ml) was added oxalylchloride (0.24 g, 0.0020 mole). This mixture was heated at reflux forfive days. Additional oxalyl chloride (0.24 g) was added and refluxingwas continued for one more day. The solvent was removed from thereaction mixture by distillation under reduced pressure, leaving an oil.This oil was purified by column chromatography on silica gel, elutionwith toluene: ethyl acetate (9:1), yielding 0.84 g of1-[(2,6-difluorophenyl)carbonyl]-3-[2-[1-(3,4-dichloophenyl)-2,2,2-trifluoroethoxy]pyridin-5-yl]imidazolidinetrioneas a solid (mp 160° C.). The nmr and ir spectra were consistent with theproposed structure.

Analysis: Calc'd for C₂₃ H₁₀ Cl₂ F₃ N₃ O₅ : C 48.11; H 1.76; Found: C47.15; H 1.69.

Additional Examples prepared by similar techniques appear in Table 1.

In the normal use of the insecticidal benzoylureas of the presentinvention, the benzoylureas usually will not be employed free fromadmixture or dilution, but ordinarily will be used in a suitableformulated composition compatible with the method of application andcomprising an insecticidally effective amount of benzoylurea. Thebenzoylureas of this invention, like most pesticidal agents, may beblended with the agriculturally acceptable surface-active agents andcarriers normally employed for facilitating the dispersion of activeingredients, recognizing the accepted fact that the formulation and modeof application of an insecticide may affect the activity of thematerial. The present benzoylureas may be applied, for example, assprays, dusts, or granules to the area where pest control is desired,the type of application varying of course with the pest and theenvironment. Thus, the benzoylureas of this invention may be formulatedas granules of large particle size, as powdery dusts, as wettablepowders, as emulsifiable concentrates, as solutons, and the like.

Granules may comprise porous or nonporous particles, such as attapulgiteclay or sand, for example, which serve as carriers for the benzoylureas.The granule particles are relatively large, a diameter of about 400-2500microns typically. The particles are either impregnated with thebenzoylurea from solution or coated with the benzoylurea, adhesivesometimes being employed. Granules generally contain 0.05-10%,preferably 0.5-5%, active ingredient as the insecticidally effectiveamount.

Dusts are admixtures of the benzoylureas with finely divided solids suchas talc, attapulgite clay, kieselguhur, pyrophyllite, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, flours, and other organic and inorganic solids whichact as carriers for the insecticide. These finely divided solids have anaverage particle size of less than about 50 microns. A typical dustformulation useful for controlling insects contains 1 parts ofbenzoylurea, such asN-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide,and 99 parts of talc.

The benzoylureas of the present invention may be made into liquidconcentrates by dissolution or emulsification in suitable liquids andinto solid concentrates by admixture with talc, clays, and other knownsolid carriers used in the pesticide art. The concentrates arecompositions containing, as an insecticidally effective amount, about5-50% benzoylurea, such asN-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide,and 95-50% inert material, which includes surface-active dispersing,emulsifying, and wetting agents, but even higher concentrations ofactive ingredient may be employed experimentally. The concentrates arediluted with water or other liquids for practical application as sprays,or with additional solid carrier for use as dusts.

Typical carriers for solid concentrates (also called wettable powders)include fuller's earth, clays, silicas, and other highly absorbent,readily wetted inorganic diluents. A solid concentrate formulationuseful for controlling insects contains 1.5 parts each of sodiumlignosulfonate and sodium laurylsulfate as wetting agents, 25 parts ofN-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide,and 72 parts of attapulgite clay.

Manufacturing concentrates are useful for shipping low melting productsof this invention. Such concentrates are prepared by melting the lowmelting solid products together with one percent or more of a solvent toproduce a concentrate which does not solidify on cooling to the freezingpoint of the pure product or below.

Useful liquid concentrates include the emulsifiable concentrates, whichare homogeneous liquid or paste compositions readily dispersed in wateror other liquid carriers. They may consist entirely of the benzoylureawith a liquid or solid emulsifying agent, or they may also contain aliquid carrier such as xylene, heavy aromatic naphthas, isophorone andother relatively nonvolatile organic solvents. For application, theseconcentrates are dispersed in water or other liquid carriers andnormally applied as sprays to areas to be treated.

Typical surface-active wetting, dispersing, and emulsifying agents usedin pesticidal formulations include, for example, the alkyl and alkylarylsulfonates and sulfates and their sodium salts; alkylamide sulfonates,including fatty methyl taurides; alkylaryl polyether alcohols, sulfatedhigher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonatedanimal and vegetable oils; sulfonated petroleum oils; fatty acid estersof polyhydic alcohols and the ethylene oxide addition products of suchesters; and the addition products of long-chain mercaptans and ethyleneoxide. Many other types of useful surface-active agents are available incommerce. The surface-active agent, when used, normally comprises about1-15% by weight of the insecticidal composition.

Other useful formulations include simple solutions of the activeingredient in a solvent in which it is completely soluble at the desiredconcentration, such as acetone or other organic solvents.

An insecticidally effective amount of benzoylurea in an insecticidalcomposition diluted for application is normally in the range of about0.001% to about 8% by weight. Many variations of spraying and dustingcompositions known in the art may be used by substituting thebenzoylureas of this invention into compositions known or apparent inthe art.

The insecticidal compositions of this invention may be formulated withother active ingredients, including other insecticides, nematicides,acaricides, fungicides, plant growth regulators, fertilizers, etc. Inusing the compositions to control insects, it is only necessary that aninsecticidally effective amount of benzoylurea be applied to plants uponwhich insects feed and whose control is desired. For most applications,an insecticidally effective amount will be about 0.1-2.0 kg/ha.

The benzoylureas of this invention were tested by incorporating thecompounds into the diet of second instar southern armyworm (Spodopteraeridania) and cabbage looper (Trichoplusia ni). The tests were conductedat rates of 200, 20, and 2 ppm, using ten larvae per replicate and tworeplicates per rate. Each test was read one day, three to five days, andsix to eleven days after infestation to determine the number dead afterat least one molt.

The test media consisted of a clay formulation (dust) of the testcompound mixed with the insect diet. The components of the test mediawere:

    ______________________________________                                                       Parts by Weight                                                ______________________________________                                        Pinto beans      12.90                                                        Wheat germ       5.68                                                         Brewer's dried yeast                                                                           3.64                                                         Ascorbic acid    0.37                                                         Methyl paraben   0.23                                                         Sorbic acid      0.11                                                         Sodium benzoate  0.00284                                                      Agar             0.71                                                         Formalin (40%)   0.23                                                         Water            76.13                                                                         100.00                                                       ______________________________________                                    

The agar was dissolved with heating in one-half the water and wasbrought to a boil. Simultaneously, all other ingredients except theformalin were placed in a blender with the remaining water and werereduced to a smooth, homogenous mixture. This mixture was added to theboiling agar. Immediately, the formalin was added with mixing.

The compounds of this invention were formulated as a dust on a claybase. The dust consisted of the following:

    ______________________________________                                        Clay Formulation    5% Dust                                                   ______________________________________                                        Test compound       5.00                                                      Base                95.00                                                     96% Attaclay                                                                  2% highly purified sodium                                                     lignosulfonate (100%)                                                         2% powdered sodium alkyl-                                                     naphthalene sulfonate (75%)                                                                       100.00                                                    ______________________________________                                    

These formulations were prepared by mixing the active ingredient (i.e.the test compound) with the dry base.

Test media containing 200 ppm of the test compound were prepared bymaking a `stock solution` from 1000 mg of a 5% dust formulation stirredwell with 5 ml of distilled water in a vial. One milliliter of the`stock solution` was added to 50 ml of warm, i.e. molten, insect diet ina plastic petri dish which was then mixed thoroughly. After cooling toroom temperature, the gelled test media were infested with test larvaeand covered.

Lower test rates were prepared by dilution of the `stock solution`according to the following table:

    ______________________________________                                        Desired Rate ml of           ml of                                            (ppm)        `stock solution`                                                                              water                                            ______________________________________                                        20           1               9                                                2            1 ml of 20 ppm solution                                                                       9                                                ______________________________________                                    

The results of diet incorporated testing are summarized in Table 2.

                                      TABLE 1                                     __________________________________________________________________________    Insecticidal N[(Alpha-perhaloalkylbenzyloxy)pyridyl]-                         N'benzoylureas                                                                 ##STR4##                                                                     Example                                                                            R.sub.A                                                                          R.sub.B                                                                             R.sub.5                                                                          R.sub.2                                                                           R.sub.3                                                                           R.sub.4   mp(°C.)                             __________________________________________________________________________    1    H  H     CH.sub.3                                                                         CF.sub.3                                                                          H   H         155-158                                    2    H  Cl    H  CF.sub.3                                                                          H   H         162-163                                    3    H  Cl    H  C.sub.2 F.sub.5                                                                   H   H         149-149.5                                  4    H  Cl    H  C.sub.3 F.sub.7                                                                   H   H         129                                        6    H  Cl    H  CF.sub.3                                                                          SC.sub.6 H.sub.5                                                                  H         161-163                                    7    H  Cl    H  C.sub.3 F.sub.7                                                                   H   SCH.sub.3 124-127                                    8    H  Cl    H  CF.sub.3                                                                          Cl  Cl        111-112                                    9    H  Cl    H  C.sub.2 F.sub.5                                                                   Cl  Cl        129-131                                    10   H  Cl    H  C.sub.3 F.sub.7                                                                   Cl  Cl        119-123                                    11   H  Cl    H  CF.sub.3                                                                          OCH.sub.2 O   116-119                                    12   H  Cl    H  C.sub.2 F.sub.5                                                                   OCH.sub.2 O   121                                        13   H  Cl    H  C.sub.3 F.sub.7                                                                   OCH.sub.2 O   145                                        14   H  Cl    H  C.sub.2 F.sub.5                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                149-154                                    15   H  Cl    H  C.sub.3 F.sub.7                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                163-163.5                                  16   H  Cl    CH.sub.3                                                                         CF.sub.3                                                                          H   H         142-145                                    17   H  Cl    CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   H   H         124-125                                    18   H  Cl    CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   H   H                                                    20   H  Cl    CH.sub.3                                                                         CF.sub.3                                                                          H   Cl        115                                        21   H  Cl    CH.sub.3                                                                         CF.sub.3                                                                          Cl  Cl                                                   22   H  Cl    CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   Cl  Cl        90-94                                      23   H  Cl    CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   Cl  Cl        131-133                                    24   H  Cl    CH.sub.3                                                                         CF.sub.3                                                                          OCH.sub.2 O                                              25   H  Cl    CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   OCH.sub.2 O   144                                        26   H  Cl    CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   OCH.sub.2 O   63                                         27   H  Cl    CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                141-143                                    28   H  Cl    CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                152-155                                    29   H  Cl    CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   Cl  N(CH.sub.2 CHCH.sub.2).sub.2                                                            oil                                        30   H  F     CH.sub.3                                                                         CF.sub.3                                                                          H   H                                                    31   H  CH.sub.3                                                                            CH.sub.3                                                                         CF.sub.3                                                                          H   H         122-123                                    32   H  C.sub.2 H.sub.5                                                                     CH.sub.3                                                                         CF.sub.3                                                                          H   H         103-104                                    33   H  CH.sub.2 C.sub.6 H.sub.5                                                            CH.sub.3                                                                         CF.sub.3                                                                          H   H         89-91                                      34   H  OCH.sub.3                                                                           CH.sub.3                                                                         CF.sub.3                                                                          H   H         139-142                                    35   H  OCH.sub.2 C.sub.6 H.sub.5                                                           CH.sub.3                                                                         CF.sub.3                                                                          H   H         104-106                                    36   F  F     H  CF.sub.3                                                                          H   H         172-174                                    37   F  F     H  C.sub.2 F.sub.5                                                                   H   H         193-195                                    38   F  F     H  C.sub.3 F.sub.7                                                                   H   H         137                                        40   F  F     H  CF.sub.3                                                                          SC.sub.6 H.sub.5                                                                  H         102-103.5                                  41   F  F     H  C.sub.3 F.sub.7                                                                   H   SCH.sub.3 132-135                                    42   F  F     H  CF.sub.3                                                                          Cl  Cl        171-172                                    43   F  F     H  C.sub.2 F.sub.5                                                                   Cl  Cl        164-167                                    44   F  F     H  C.sub.3 F.sub.7                                                                   Cl  Cl        158-160                                    45   F  F     H  CF.sub.3                                                                          OCH.sub.2 O   165-167                                    46   F  F     H  C.sub.2 F.sub.5                                                                   OCH.sub.2 O   183                                        47   F  F     H  C.sub.3 F.sub.7                                                                   OCH.sub.2 O   103                                        48   F  F     H  CF.sub.3                                                                          CH.sub.2 C(CH.sub.3).sub.2 O                                                                122                                        49   F  F     H  C.sub.2 F.sub.5                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                163-167                                    50   F  F     H  C.sub.3 F.sub.7                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                164-167                                    51   F  F     H  CF.sub.3                                                                          CF.sub.2 CF.sub.2 O                                                                         162-163.5                                  52   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   H         143-145                                    53   F  F     CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   H   H         121-122                                    54   F  F     CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   H   H         102                                        56   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   Cl        145                                        57   F  F     CH.sub.3                                                                         CF.sub.3                                                                          Cl  Cl                                                   58   F  F     CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   Cl  Cl        119-122                                    59   F  F     CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   Cl  Cl        132-132.5                                  60   F  F     CH.sub.3                                                                         CF.sub.3                                                                          OCH.sub.2 O   167                                        61   F  F     CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   OCH.sub.2 O   144                                        62   F  F     CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   OCH.sub.2 O   94                                         63   F  F     CH.sub.3                                                                         CF.sub.3                                                                          CH.sub.2 C(CH.sub.3).sub.2 O                                                                115                                        64   F  F     CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                135-140                                    65   F  F     CH.sub.3                                                                         C.sub. 3 F.sub.7                                                                  CH.sub.2 C(CH.sub.3).sub.2 O                                                                140-143                                    66   F  F     CH.sub.3                                                                         CF.sub.3                                                                          CF.sub.2 CF.sub.2 O                                                                         oil                                        67   Cl F     CH.sub.3                                                                         CF.sub.3                                                                          H   H         171-175                                    68   Cl CH.sub.3                                                                            CH.sub.3                                                                         CF.sub.3                                                                          H   H         164-167                                    69   F  F     H  CClF.sub.2                                                                        H   H         191-192                                    70   F  F     CH.sub.3                                                                         CClF.sub.2                                                                        H   H         107-110                                    71   F  F     CH.sub.3                                                                         C.sub.3 F.sub.7                                                                   Cl  N(CH.sub.2 CHCH.sub.2).sub.2                                                            oil                                        72   F  F     CH.sub.3                                                                         CClF.sub.2                                                                        F   CH.sub.3  163-165                                    73   H  3-F   CH.sub.3                                                                         CF.sub.3                                                                          H   H         180-181                                    74   H  4-F   CH.sub.3                                                                         CF.sub.3                                                                          H   H                                                    77*  H  Cl    H  CF.sub.3                                                                          H   SC.sub.6 H.sub.5                                     78*  H  Cl    H  C.sub.3 F.sub.7                                                                   H   SCH.sub.3                                            79*  H  Cl    H  CF.sub.3                                                                          Cl  Cl        149-152                                    80*  H  Cl    H  CF.sub.3                                                                          OCH.sub.2 O   134                                        81*  H  Cl    CH.sub.3                                                                         CF.sub.3                                                                          H   H                                                    82*  H  Cl    CH.sub. 3                                                                        C.sub.2 F.sub.5                                                                   H   H                                                    83*  F  F     H  C.sub.3 F.sub.7                                                                   H   SCH.sub.3                                            84*  F  F     H  CF.sub.3                                                                          Cl  Cl        160                                        85*  F  F     H  CF.sub.3                                                                          OCH.sub.2 O   164                                        86*  F  F     H  C.sub.2 F.sub.5                                                                   CH.sub.2 C(CH.sub.3).sub.2 O                                                                184                                        87*  F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   H         67                                         88*  F  F     CH.sub.3                                                                         C.sub.2 F.sub.5                                                                   H   H                                                    89   Cl H     CH.sub.3                                                                         CF.sub.3                                                                          H   OC.sub.2 H.sub.5                                                                        167                                        90   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   OC.sub.2 H.sub.5                                                                        137                                        91   Cl H     CH.sub.3                                                                         CF.sub.3                                                                          H   CH.sub.2 OCH.sub.3                                                                      163-167                                    92   Cl H     CH.sub.3                                                                         CF.sub.3                                                                          H   SCH.sub.3 151                                        93   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   SCH.sub.3 151                                        94   Cl H     CH.sub.3                                                                         CF.sub.3                                                                          H   SO.sub.2 CH.sub.3                                                                       134                                        95   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   SO.sub.2 CH.sub.3                                                                       180                                        96   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   OCF.sub.3 161                                        97   Cl H     CH.sub.3                                                                         CF.sub.3                                                                          H   OCF.sub.3 139                                        98   F  F     CH.sub.3                                                                         CF.sub.3                                                                          H   CH.sub.2 OCH.sub.3                                                                      140-144                                    __________________________________________________________________________     *R.sub.C and R.sub.D together constitute a COCObridge.                   

                  TABLE 2                                                         ______________________________________                                        Diet Incorporated Tests                                                       % Kill                                                                        (5% Formulation on Clay)                                                      Exposure   Insects Tested.sup.a and Rate                                      Cpd. of                                                                             Period   SAW (ppm)       CL (ppm)                                       Ex.   (Days)   200     20    2     200  20    2                               ______________________________________                                        1     5        100     100   0     100   100  10                              2     4        70      80    60    100   100  90                              3     5        100     100   100   100   100  80                              4     4        90      90    90    100   100  80                              6     4        100     0     10    20    0    0                               7     4        100     70    0     60    10   0                               8     4        0       50    70    100   100  0                               9     3        60      100   30    100   70   0                               10    4        90      100   70    100   0    0                               11    8        20      0     0     100   100  0                               12    6        60      10    0     100   60   20                              13    5        90      30    0     90    40   0                               14    6        10      100   0     90    10   0                               15    7        100     100   90    100   40   0                               16    5        90      100   100   100   100  100                             17    5        100     100   100   100   100  100                             18    4        70      100   0     100   100  0                               20    4        100     100   100   100   100  90                              21    4        10      60    0     80    0    0                               22    7        100     100   60    100   90   10                              23    4        100     80    60    80    0    0                               24    4        60      50    0     10    80   10                              25    3        0       50    0     90    40   0                               26    6        80      60    0     100   40   10                              27    8        100     60    0     100   70   0                               28    4        100     80    30    50    0    0                               29    8        10      30    10    10    0    0                               30    4        100     80    20    90    100  30                              31    5        100     100   100   100   100  20                              32    8        50      10    0     0     0    0                               33    8        0       0     0     0     0    10                              34    5        100     0     0     0     0    10                              35    8        30      0     0     10    0    0                               36    4        70      80    60    100   100  90                              37    5        100     90    100   100   100  100                             38    7        90      100   100   90    100  100                             40    5        30      50    10    90    80   0                               41    5        100     100   0     100   100  10                              42    4        60      60    90    80    100  80                              43    3        80      90    60    100   80   30                              44    4        100     100   100   100   100  0                               45    5        10      10    20    90    80   10                              46    6        100     100   0     100   100  0                               47    5        30      50    10    90    80   0                               48    4        100     100   80    90    80   80                              49    8        100     100         50    60   10                              50    4        90      100   60    100   100  0                               51    5        100     100   100   100   100  100                             52    5        100     100   100   100   100  100                             53    5        90      100   100   100   100  100                             54    4        70      90    100   100   100  100                             56    4        100     100   100   80    90   70                              57    4        40      70    90    20    40   0                               58    7        100     100   90    100   100  10                              59    4        100     100   90    100   100  10                              60    4        30      30    0     90    30   0                               61    3        10      50    10    100   80   0                               62    6        70      50    0     100   90   0                               63    4        100     100   70    80    100  80                              64    2        20      0     0     40    40   0                               65    4        100     100   50    100   30   0                               66    4        60      70    100   100   100  90                              67    4        100     100   100   90    100  40                              68    5        100     100   0     100   100  10                              69    4        100     100   80    100   100  100                             70    4        90      100   90    100   100  80                              71    8        70      20    30    0     0    10                              72    5        100     100   60    100   80   70                              73    4        0       10    0     0     0    0                               74    4        70      0     0     20    10   10                              77    4        80      0     0     100   0    0                               78    4        100     0     0     100   0    0                               79    9        100     100   40    100   100  20                              80    8        0       70    20    100   30   0                               81    5        100     100   0     100   90   0                               82    5        90      100   10    100   100  0                               83    4        100     100   0     100   80   0                               84    4        100     90    40    100   80   0                               85    8        90            10    100   40   10                              86    8        60      0     10    50    0    0                               87    3        70      80    100   100   90   80                              88    5        100     100   10    90    90   70                              89    5                            100   85.sup.b                                                                           75.sup.c                        90    5                            100   l00.sup.b                                                                          l00.sup.c                       91    5                            100   90.sup.b                                                                           45.sup.c                        92    5                            100   0    0                               93    5                            100   15   0                               94    5                            95    10   0                               95    5                            95    25   0                               96    5                            100   100  75                              97    5                            100   100  100                             98    5                            100   95.sup.b                                                                           50.sup.c                        ______________________________________                                         .sup.a SAW = Southern armyworm CL = Cabbage looper                            .sup.b 10 ppm                                                                 .sup.c 5 ppm                                                             

What is claimed is:
 1. An insecticidal benzoylurea compound of theformula ##STR5## wherein R_(A) is selected from the group consisting of-hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and-benzyloxy;R_(B) is selected from -hydrogen and -halogen; R_(C) andR_(D) are both -hydrogen; R.sub.α is a lower perhaloalkyl substituent;R₃ is selected from the group consisting of -hydrogen, -halogen and-phenylthio; R₄ is selected from the group consisting of -hydrogen,-halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lowerhaloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino;R₅ is -hydrogen or -lower alkyl. 2.N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide,a compound of claim
 1. 3.N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-fluorobenzamide,a compound of claim
 1. 4.N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,a compound of claim
 1. 5.N-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,a compound of claim
 1. 6.N-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide,a compound of claim
 1. 7.N-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide,a compound of claim
 1. 8. An insecticidal composition comprising inadmixture with an agriculturally acceptable carrier a of the formula##STR6## wherein R_(A) is selected from the group consisting of-hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and-benzyloxy;R_(B) is selected from -hydrogen and -halogen; R_(C) andR_(D) are both -hydrogen; R.sub.α is a lower perhaloalkyl substituent;R₃ is selected from the group consisting of -hydrogen, -halogen and-phenylthiol; R₄ is selected from the group consisting of -hydrogen,-halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lowerhaloalkyoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino;R₅ is -hydrogen or -lower alkyl.
 9. An insecticidal composition of claim8 wherein said compound isN-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide.10. An insecticidal composition of claim 8 wherein said compound isN-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide.11. An insecticidal composition of claim 8 wherein said compound isN-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide.12. A method for controlling insects which comprises applying to plantsupon which insects feed and whose control is desired an insecticidallyeffective amount of a compound of the formula ##STR7## wherein R_(A) isselected from the group consisting of -hydrogen, -halogen, -lower alkyl,-lower alkoxy, -benzyl, and -benzyloxy;R_(B) is selected from -hydrogenand -halogen; R_(C) and R_(D) are both -hydrogen;R.sub.α is a lowerperhaloalkyl substituent; R₃ is selected from the group consisting of-hydrogen, -halogen and -phenylthio; R₄ is selected from the groupconsisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -loweralkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl,and -diallylamino; R₅ is -hydrogen or -lower alkyl.
 13. The method ofclaim 12 wherein said compound isN-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-3-chlorobenzamide.14. The method of claim 12 wherein said compound isN-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide.15. The method of claim 12 wherein said compound isN-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide.